Thermoplastic epoxy materials with core shell phase

ABSTRACT

A composite article (30), comprising at least one fibrous layer (12), and at least one thermoplastic epoxy web layer (14) located in direct planar contact with the at least one fibrous layer (12), the at least one thermoplastic epoxy web layer (14) being adapted to substantially phase separate during a molding and/or curing process.

TECHNICAL FIELD

The present invention relates generally to thermoplastic epoxymaterials, particularly to materials having a thermoplastic epoxy-basedmatrix and a core-shell phase dispersed in the matrix.

BACKGROUND

There is an ongoing effort in many industries to lighten the weight ofarticles. In many instances, this is achieved by the selection ofmaterials that have a lower density, thinner section thicknesses, orboth, as compared with prior materials or structures. Compositematerials are often employed. As a result, there is a potential for theweakening of structures, and the consequent need for stiffening or otherstructural reinforcement. As new, lightweight materials are employed,there is an additional need for improved adhesives/bonding materialsthat are compatible with such lightweight materials while providing forsufficient bonding within the composite material layers. As an example,polymeric stitching fibers (e.g., PET fibers) have been utilized to formfibrous composites. However, such fibers are still visible on thecomposite surface post molding and curing.

There is a further need for the ability to incorporate various additivesinto adhesive/bonding materials without any deleterious effect on theviscosity of those materials. As one specific example, there may be adesire to incorporate one or more additives that act to toughen thebonding material. A toughening additive is desirable that will enhanceimpact and damage resistance properties of the composite withoutadversely affecting other material properties. In the event that thetoughening agent is included in a resin during resin infusion in amolding process, the viscosity of the resin will be increased due to theincorporation of the toughening agent. Increased viscosity requires moretime to complete the resin infusion and can also cause the fibers withinthe composite to be moved out of position.

There is also a need for the ability to improve lap shear strength whena thermoplastic epoxy material (e.g., a toughened thermoplastic epoxymaterial) is employed for bonding to a substrate.

Notwithstanding the above efforts there remains a need for alternativeadhesive/bonding layer materials that impart structural rigidity andbond strength. There remains a need for alternative adhesive/bondinglayer materials with minimal surface topographical variations on theresulting materials. There is a further need for adhesive/bonding layermaterials that can be formed to contain additional additives which mayoptionally be released upon molding and/or curing of the resultingcomposite. There is also a need for alternative carrier structures thatemploy a combination of different materials that, even though they aredissimilar, are still generally compatible (e.g., chemically and/orphysically compatible) with each other.

Examples of composite structures are illustrated in PCT Application No.WO 2007/008569, United States Published Patent Application Nos.2011/0039470 and 2012/0251863, and U.S. Pat. No. 7,581,932 allincorporated by reference for all purposes. See also, U.S. Pat. Nos.6,855,652, 7,125,461 and 7,318,873, and United States Published PatentApplication Nos. 2003/0039792, 2010/0289242, 2011/0278802, and2009/0202294, incorporated by reference for all purposes.

The present application also is related to and incorporates by referencefor all purposes Great Britain Patent Application No. 1318595.4, filedOct. 21, 2013.

Further to the above, thermoplastic polymers having at least one epoxidegroup have been described in U.S. Pat. Nos. 5,115,075; 4,438,254;6,011,111; and WO 98/14498 (see e.g., pages 3-8) along with illustrativesynthesis conditions, all incorporated by reference herein (see alsoU.S. Pat. Nos. 3,317,471 and 4,647,648, also incorporated by referenceherein). Examples of such materials also can be found, withoutlimitation at paragraphs 15-25 of Published U.S. Patent Application No.20070270515 (Chmielewski et al), incorporated by reference for allpurposes.

The use of such thermoplastic polymers in a composite material has beendisclosed in WIPO Patent Application WO/2008/010823 (addressing in situreaction of an epoxy and an amine after impregnation), incorporated byreference herein. Notwithstanding the above, there remains a need foralternative composite materials. For example, there remains a need forcomposite materials that are suitable for use in or otherwise with acarrier for a baffle and/or structural reinforcement for atransportation vehicle of a type exemplified in the above discussedpatent publications.

SUMMARY OF THE INVENTION

One or more of the above needs are met by the present teachings whichcontemplate a multi-phase polymeric material, at least one first phaseof the material including a thermoplastic epoxy material, and at leastone second phase including a core-shell polymeric phase. The at leastone first or second phases may be interspersed in the other of the atleast one first or second phases (e.g., selectively in a predeterminedmanner, in a random manner, in a generally uniform manner, a generallynon-uniform manner, or any combination thereof). The thermoplasticmaterial may be any thermoplastic epoxy material of a type described inthe literature. By way of example, one such class of thermoplastic epoxymaterials may be described generally as a reaction product of at leastone diepoxide resin and at least one mono primary amine or di-secondaryamine. The thermoplastic epoxy material may include ahydroxy-phenoxyether polymer reaction product (e.g., a polyetheraminethermoplastic material) of a mono-functional or di-functional specieswith an epoxide-containing moiety, such as a diepoxide, reacted underconditions for causing the hydroxyl moieties to react with the epoxymoieties to form a generally linear backbone polymer chain with etherlinkages.

The at least one second phase may include a core-shell polymeric phase.In general, such phase may include a plurality of particulates that havean elastomeric core adapted to impart impact resistance to the material,and a shell that is chemically adapted to be compatible with the polymerof the at least one first phase. By way of illustration, usefulcore-shell graft copolymers may be those where materials such asstyrene, acrylonitrile or methyl methacrylate may be grafted onto a coremade from polymers of soft or elastomeric compounds such as butadiene orbutyl acrylate.

In a general sense, the teachings relate to a toughened thermoplasticepoxy polymeric material, comprising a thermoplastic epoxy matrix firstphase; and from greater than 0% by weight up to about 10% by weight, orup to about 20% by weight, of a discrete particulated second phase of acore shell toughening agent dispersed throughout the first phase, andbeing separable from the first phase.

In one approach to the teachings herein, the thermoplastic epoxypolymeric material may be employed as part of a composite article. Thecomposite article may be transformed during subsequent processing stepsto cause separation of the thermoplastic epoxy matrix first phase; andthe discrete particulated second phase of the core shell tougheningagent. For example, the composite article may comprise at least onefibrous layer and at least one thermoplastic epoxy web layer located incontact with the at least one fabric layer, the at least onethermoplastic epoxy web layer being adapted to substantially dissolve(that is, a skilled artisan would recognize that the at least onethermoplastic epoxy web layer would transform to a fluidic state foraffording phase separation as between the two phases) during a moldingand/or curing process. The fabric may have a volume and sufficientporosity, in size and amount, to permit the entrance of particulates ofthe particulated second phase to one or more locations within the volumeof the fabric.

The composite article may be substantially free of any liquid or powderadhesive and/or bonding material. The thermoplastic epoxy web layer maymelt into an adjacent layer during a molding and/or curing process. Thethermoplastic epoxy web layer may comprise an additive that is releasedinto the composite article during a molding and/or curing step. Thethermoplastic epoxy web layer may comprise a toughening agent (e.g., acore shell polymer) that is released into the composite article during amolding and/or curing step. An additive may be embedded within thethermoplastic epoxy web layer. The at least one fibrous layer maycomprise a carbon fiber material. The thermoplastic epoxy web layer maybe formed as a reaction product of diepoxide resin and a mono primaryamine or a di-secondary amine. The thermoplastic epoxy web may include ahydroxy-phenoxyether polymer reaction product (e.g., a polyetheraminethermoplastic material) of a mono-functional or di-functional specieswith an epoxide-containing moiety, such as a diepoxide, reacted underconditions for causing the hydroxyl moieties to react with the epoxymoieties to form a generally linear backbone polymer chain with etherlinkages. The composite article may include an epoxy resin injectedabout the one or more fibrous layers and one or more thermoplastic epoxywebs during a molding process.

The teachings herein further provide for a method of making athermoplastic epoxy material (e.g., in a suitable form, such as anextrudate, a molded form, a web or a combination of two or more of each)comprising dispersing a particulated toughening agent in a monomericliquid phase epoxy resin, polymerizing the epoxy resin withmonoethanolamine to form a thermoplastic reaction product (which may bea condensation product) having a dispersion (e.g., a substantiallyhomogeneous dispersion) of the particulated toughening agent therein.Optionally, the thermoplastic reaction product having a dispersion ofthe particulated toughening agent therein may be processed for formingthe desired form. For example, it may be subjected to injection moldingor other molding to form a thermoplastic epoxy molded form, extrusion toform an extrudate, and/or melt blowing, melt spinning, electrospinningor employing a wet laid process utilizing the reaction product to obtaina thermoplastic epoxy web that includes a thermoplastic epoxy phase anda discrete and separable particulated toughening agent phase.

It is possible that the resulting forms are employed in combination withother forms to define a composite articles. For instance one or more ofthe resulting forms may be located proximate of a mass of a material ina manner for transferring the particulated toughening agent locatedtherein from the resulting form to the mass of material, such as by aphase separation occasioned by heating the resulting form to one or moretemperature thermoplastic epoxy material to become fluidic, while theparticulates of the toughening agent remain solid. This can be achieved,for example, by heating to a temperature above the glass transitiontemperature (or melting point) of the thermoplastic epoxy material butbelow the glass transition temperature (or melting point) of thetoughening agent particulates. The method may further include locatingthe thermoplastic epoxy web in contact (e.g., in direct contact) withone or more fibrous layers to form a composite article. The method mayalso include melting the thermoplastic epoxy web within an adjoiningmass of epoxy resin so that the dispersed particulate toughening agentremains in place, in contact with the one or more fibrous layers. Thenresulting form of the thermoplastic epoxy material may be formed havingamine end groups and tertiary amines which react with the epoxy resin toincrease cohesion between the one or more fibrous layers.

The teachings herein also provide for a composite comprising at leastone first material layer selected from a tape material, a fibrousmaterial, or a polymeric material having an outer surface, and at leastone second material layer located in between and in direct planarcontact with each of the at least one first material layers, wherein theat least one second material layer is thermoplastic epoxy web comprisinga hydroxy-phenoxyether polymer, such as a polyetheramine thermoplasticmaterial, which is a product (e.g., a thermoplastic condensationreaction product) of a reaction of a mono-functional or di-functionalspecies (e.g., monoethanolamine) with an epoxide-containing moiety, suchas a diepoxide (e.g., diglycidyl ether bisphenol A) reacted underconditions for causing the hydroxyl moieties to react with the epoxymoieties to form a generally linear backbone polymer chain with etherlinkages. The composite may also include exactly one second materiallayer. The composite may include exactly two first material layers.

The teachings herein are also directed to a prepreg material including athermoplastic epoxy web present during formation of the prepreg, butintegrated into the prepreg material during a curing process. Theprepreg material may include a carbon fiber material.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic of a system for making an article in accordancewith the present teachings.

FIG. 2 is an exploded view of an exemplary composite in accordance withthe teachings herein.

FIG. 3 is a schematic of a system for making an article in accordancewith the present teachings.

DETAILED DESCRIPTION

The present teachings meet one or more of the above needs by theimproved devices and methods described herein. The explanations andillustrations presented herein are intended to acquaint others skilledin the art with the teachings, its principles, and its practicalapplication. Those skilled in the art may adapt and apply the teachingsin its numerous forms, as may be best suited to the requirements of aparticular use. Accordingly, the specific embodiments of the presentteachings as set forth are not intended as being exhaustive or limitingof the teachings. The scope of the teachings should, therefore, bedetermined not with reference to the above description, but shouldinstead be determined with reference to the appended claims, along withthe full scope of equivalents to which such claims are entitled. Thedisclosures of all articles and references, including patentapplications and publications, are incorporated by reference for allpurposes. Other combinations are also possible as will be gleaned fromthe following claims, which are also hereby incorporated by referenceinto this written description.

The present application claims the benefit of the filing dates of U.S.Provisional Application No. 62/280,934, filed Jan. 20, 2016; and62/372,551, filed Aug. 9, 2016, the contents of these applications beinghereby incorporated by reference herein for all purposes.

The teachings herein are predicated generally upon the employment incombination of a thermoplastic epoxy material and a core-shellparticulated toughening agent.

In one general reaction, the thermoplastic epoxy material may be areaction product of a diglycidyl ether of a dihydroxy organic compound)and an amino, namely one having two amino hydrogens per molecule (e.g.,a reaction product of a diglycidyl ether of bisphenol A and amonoethanolamine), as described for example at col. 1, line 4 throughcol. 2, line 52 in U.S. Pat. No. 3,317,471 (incorporated by reference).Stated another way, the thermoplastic epoxy polymeric material may be aproduct (e.g., a thermoplastic condensation reaction product) of areaction of a mono-functional or di-functional species (i.e.,respectively, a species having one or two reactive groups, such as anamide containing species), with an epoxide-containing moiety, such as adiepoxide (i.e., a compound having two epoxide functionalities), reactedunder conditions for causing the hydroxyl moieties to react with theepoxy moieties to form a generally linear backbone polymer chain withether linkages.

The thermoplastic epoxy material may be any of the thermoplastic epoxymaterials described in the literature. Examples include:

(a) a reaction product of diglycidyl ether of a bisphenol with adihydroxybiphenyl, in which the repeating unit of the polyhydroxyethercontains a hydrocarbon connecting group and a hydrocarbon or halogensubstituted phenylene radical, as described in U.S. Pat. No. 4,647,648(incorporated by reference);

(b) a reaction product of a diglydicyl ether of certain amido-dihydricphenols and N-substituted dihydric phenols, as described in U.S. Pat.No. 5,115,075 (incorporated by reference);

(c) a reaction product of a dihydric phenol (e.g., a diglycidyl ether ofone or more of bisphenol ketone, bisphenol sulfone, resorcinol, orhydroquinone) and at least one other dihydric phenol such as4,4′-ispropylidene bisphenol (bisphenol A),4,4′-dihydroxydiphenylethylmethane,3,3′-dihydroxydiphenyldiethylmethane,3,4′-dihydroxydiphenylmethylpropylmethane, bisphenol,4,4′-dihydroxydiphenyloxide, 4,4′-dihydroxydiphenylcyanomethane,4,4′-dihydroxybiphenyl, 4,4′-dihydroxybenzophenone,4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxydiphenyl sulfone,2,6-dihydroxynaphthalene, 1,4′-dihydroxynaphthalene, catechol, or thelike, as described in U.S. Pat. No. 5,164,472 (incorporated byreference);

(d) a reaction product (e.g., a reactive extrusion product) of adiglycidyl ether of a dihydric phenol with an amine having only twohydrogens under conditions sufficient to form the polyetheramine, asdescribed in U.S. Pat. No. 5,275,853 (incorporated by reference);

(e) a reaction product of dihydric phenol and a diepoxide in thepresence of a catalyst selected frombis(trihydrocarbylphosphoranylidene)ammonium salt,bis[tris(dihydrocarbylam ino)phosphoranylidene]ammonium salt, ortetrakis[tris(dihydrocarbylamino)phosphoranylideneamino]phosphoniumsalt, as described in U.S. Pat. No. 5,401,814 (incorporated byreference);

(f) a reaction product prepared by reacting (1) a primary amine orbis(secondary) diamine with (2) a diglycidyl ether and (3) an amine- orepoxy-functionalized poly(alkylene oxide), as described in U.S. Pat. No.5,464,924 (incorporated by reference);

(g) a reaction product of a compound having an average of more than onevicinal epoxide group per molecule and a polyhydric phenol orthiophenol, in the presence of a catalytic amount of a tetrahydrocarbylphosphonium salt in an essentially anhydrous medium, as described inU.S. Pat. No. 4,438,254 (incorporated by reference);

(h) a reaction product of a diepoxide (e.g., diglycidyl ethers ofdihydric phenols) and a difunctional species selected from dihydricphenols, dicarboxylic acids, bis-secondary amines, primary amines,dithiols, disulfonamides, and compounds that contain two differentfunctionalities capable of reacting with epoxide groups, as described inU.S. Pat. No. 6,011,111 (incorporated by reference); or

(i) a hydroxy-phenoxyether reaction product polymer prepared by reactinga difunctional species (that is, a species having two reactive groups),such as a dihydric phenol, with a diepoxide (that is, a compound havingtwo epoxide functionalities) under conditions sufficient to cause thehydroxyl moieties to react with the epoxy moieties to form etherlinkages, as described in WO98/14498 (incorporated by reference).

The teachings herein may also be employed with a thermoplastic epoxymaterial a reaction employed to result in a thermoplastic epoxy polymerthat is essentially devoid of nitrogen and/or an amine moiety along itsbackbone. The reaction product may have a relatively high glasstransition temperature, which may be derived from a reaction of at leastone diepoxide and at least one bisphenol. The at least one diepoxide(e.g., at least one diglycidyl ether) and at least one bisphenol arereacted (in molar amounts) in a ratio of the at least one diepoxide tothe at least one bisphenol in a ratio of about 4:1 to about 1:4 (e.g.,about 2:1 to about 1:2, or even about 1:1). In regard to the ingredientsof a reaction mixture, the at least one diepoxide may have a molecularweight ranging from about 130 to about 460 g/mol (e.g., about 220 toabout 350). The at least one diepoxide may include at least one etherlinkage. The at least one diepoxide may include at only two etherlinkages. The at least one diepoxide may include at least one, two ormore phenyl moieties. For example, it may have only two phenyl moieties.The at least one diepoxide may include at least one ether linkagebetween at least one phenyl moiety and an epoxide functional group. Thediepoxide may be selected from resorcinol diglycidyl ether, diglycidylether of bisphenol A (“DGEBA”), bisphenol F diglycidyl ether, bisphenolA propoxylate diglycidyl ether, or any combination thereof. The materialof the present teachings may employ as its at least one bisphenolingredient a bisphenol that has a molecular weight of about 200 to about360 g/mol. The at least one bisphenol may be selected from4,4′-(1-phenylethylidene) bisphenol; 4,4′-sulfonylbisphenol; or acombination thereof.

It is contemplated that where fire resistance is desired, some or all ofthe reactants may employ a brominated reactant. For example, a reactantsuch as a diglycidyl ether of a bisphenol may be replaced by abrominated bisphenol epoxy resin.

The core-shell particulates referenced herein may include an elastomericcore (e.g., a cross-linked rubber core). The elastomeric core, forexample, may include butadiene. The elastomeric core may include acopolymer of butadiene and styrene. The elastomeric core may include apolymer having at least one silicon atom (e.g., a silicone rubber). Thecore shell particulates may include a shell that includes a(meth)acrylic acid, an ester thereof, and or a nitrile thereof. Forexample, the particulates may include a copolymer, such as a copolymerof styrene, methyl methacrylate, glycidyl methacrylate and optionallyacrylonitrile. The core-shell particulates may be dispersed in a liquidsuspension medium in a range of concentrations (e.g., from about 5% toabout 50%, such as about 10% to about 40% by weight of the totaldispersion). The core-shell particulates may be dispersed in a liquidsuspension medium that may include a liquid resin, such as an epoxybased resin (e.g., diglycidyl ether of bisphenol A, diglycidyl ether ofbisphenol F, a reaction product of one or both with another ingredient(such as epichlorohydrin), or any combination of these materials).Examples of commercially available core-shell particulates include thosesold by Kaneka Corporation under the designation Kaneka Kane Ace, (e.g.,grade 136 (dispersed as a concentrate in a diglycidyl ether of bisphenolF; and/or grade 156 (dispersed as a concentrate in a diglycidyl ether ofbisphenol A). For additional guidance, the teachings of U.S.2007/0027233 may be employed. The liquid suspension medium may be suchthat the particulates require no separation therefrom prior to mixingwith other reactants. Thus, it is possible that the liquid suspensionmedium will form part of the reactants to form the resulting materialsof the present teachings.

The core shell particulates may be characterized by one or more of theirphysical characteristics. For example, the particulates may be generallyspherical. They may have an average diameter of about 0.01 micrometersto about 1 micrometers (e.g., about 0.05 to 0.2 micrometers), measuredby scanning electron microscopy. Thus, the core-shell particles may beof generally nanoparticle sizes.

The core shell particulates may be employed in an amount relative to thetotal amount of the core shell particulates and the thermoplastic epoxymaterial of up to about 20 percent by weight, up to about 15 percent byweight, up to about 10 percent by weight. The core shell particulatesmay be employed in an amount relative to the total amount of the coreshell particulates and the thermoplastic epoxy material of at leastabout 1 percent by weight, at least about 3 percent by weight, or atleast about 5 percent by weight.

The multi-phase materials of the present teachings are made by preparingone or more mixtures of reactants that include the reactants for makingthe thermoplastic epoxy material and a source of the core-shellparticulates. The source of the core-shell particulates, as gleaned fromthe above, may include a suspension medium that is also introduced intothe mixture of reactants. The suspension medium may, for instance,include DGEBA, DGEBF or both. The mixture of reactants may thus includethe thermoplastic epoxy material reactants, core-shell particulates, andthe suspension medium (e.g., DGEBA, DGEBF or both). The mixture ofreactants may then be mixed.

Another possible approach may be to employ an adduct that includes anelastomer. The elastomer adduct imports flexibility and the ability toinitiate plastic deformation to the thermoplastic web and any substratereceiving the thermoplastic web. Various epoxy/elastomer adducts may beemployed in the present teachings. The elastomer-containing adduct maybe a combination of two or more particular adducts and the adducts maybe solid adducts, liquid adducts or semisolids at a temperature of 23°C. or may also be combinations thereof. The adduct may be used togetherwith the core/shell impact modifiers described herein, such asmethacrylate-butadiene-styrene (MBS), and another modifier, such aspolyvinyl butyral (PVB), which may achieve desirable adhesiveperformance over a wide range of temperatures, even when employing arelatively small amount of the adduct. A lower amount of adduct such as5% to 15% by weight imparts high temperature stability to thethermoplastic web since there is little undesirable lowering of theglass transition temperature (Tg) of the formulation.

The teachings herein further provide for a multi-phase thermoplasticepoxy material (including core-shell particulates) as described herein.It can take any of a number of different forms, such as a shaped moldedarticle, a sheet, an elongated extrudate with a common shaped profile, atube, a rod, or the like. One approach envisions a web material, namelya relatively flat constant profile elongated form. The web material mayinclude pores and/or a predetermined arrangement of openings, or otherpredetermined surface topography. The web material, or other forms moregenerally, may have a thickness of less than about 10 mm, less thanabout 7 mm, less than about 5 mm, or less than about 3 mm. It may have athickness of more than about 0.01 mm, more than about 0.1 mm, or morethan about 1 mm.

The multi-phase thermoplastic epoxy material (e.g., the thermoplasticweb material layer) is employed in a manner so that is can dissolve intoan adjacent layer or other mass of another material, which may occurduring a molding step, a curing step, or some other step involvingapplication of heat. The skilled artisan will appreciate from theteachings that reference to dissolution refers to a separation of phasesof the multi-phase thermoplastic epoxy material; i.e., a thermoplasticepoxy phase separates from the core-shell particulates, such as bychanging to a fluidic state while the core-shell particulates remain ina generally solid state.

By way of one example, an initial multi-phase thermoplastic epoxymaterial (e.g., the thermoplastic web material layer) may be employed ina manner so that the thermoplastic epoxy matrix becomes fluidic andinfiltrates a fibrous mass having a volume. As it infiltrates thefibrous mass, the fluidic material may transport some or all of thecore-shell particulates along with it and into a volume of the fibrousmass. Thus, the core-shell particulates may end up located within thefibrous mass volume. The core-shell particulates may end up locatedwithin the fibrous mass volume and bonded to one or more fibers of thefibrous mass with the thermoplastic epoxy material from the matrix ofthe initial multi-phase thermoplastic epoxy material.

It can be seen that the fibrous mass can have its properties enhancedusing the materials herein. For example, it is possible that upondissolution of the initial multi-phase thermoplastic epoxy material(e.g., web layer), the adjacent body (e.g., a fibrous mass such as alayer) receiving the constituents that were originally part of theinitial multi-phase thermoplastic epoxy material may be imparted withcertain characteristics, including but not limited to, strength,toughness, adhesion, rigidity, or the like. As an additional benefit, itis possible that additive materials may be deposited in the initialmulti-phase thermoplastic epoxy material (e.g., web) and those additivesbecome part of the adjacent body (e.g., a fibrous mass such as a layer)upon phase separation of the initial multi-phase thermoplastic epoxymaterial.

Traditionally, such additives would be added within a resin that isinjected about the layers during a molding process. However, addition ofsome additives to a resin may have unwanted effects on the resin, suchas modification of the viscosity of the resin. Thus, by including suchadditives in the web layer, there is no need to modify the resin, yetthe final composite structure has the benefit of the additive upon suchphase separation. Example additives may include but are not limited totoughening additives (e.g., core-shell materials, nano particles),curing agents and/or accelerators, fillers, or the like.

As noted, the present teachings relate generally to composite materials.In this regard, there are various composites to which the teachingspertain. The composites share the common characteristic that they eachemploy a thermoplastic epoxy material layer which is adapted to dissolve(e.g., is adapted to be integrated into an adjacent material layer)during formation of the composite. The thermoplastic epoxy web materialhas at least one epoxide group. The thermoplastic polymeric materialhaving at least one epoxide group may be a hydroxy-phenoxyether polymer,such as a polyetheramine thermoplastic material as described herein. Forexample, such thermoplastic polymeric material having at least oneepoxide group may be a product (e.g., a thermoplastic condensationreaction product) of a reaction of a mono-functional or di-functionalspecies (i.e., respectively, a species having one or two reactivegroups, such as an amide containing species), with an epoxide-containingmoiety, such as a diepoxide (i.e., a compound having two epoxidefunctionalities), reacted under conditions for causing the hydroxylmoieties to react with the epoxy moieties to form a generally linearbackbone polymer chain with ether linkages.

The composite materials may include fibrous material layers adjacent thethermoplastic epoxy web. Though referred to herein as fibrous layers, itis possible that the fibrous layers are not formed of a fibrousmaterial, but are instead formed of any material capable of absorbingthe web layer upon dissolution if the web layer. The composite articlesmay be in a form suitable for use as part for a transportation vehicle.The composite article may be in a form suitable for use as a panelstructure. The composite article may be in a form suitable for use as abuilding construction material, as a furniture material, as a sportinggood material or as protective gear material. For fibrous materiallayers employed herein, the fibers may be employed in the form of arandom distribution, a weave, a non-woven mat, a plurality of generallyaxially aligned fibers (e.g., a tow), a plurality of axially intertwinedfibers (e.g., a yarn) or any combination thereof. A plurality ofindividual fibers may thus be in a generally ordered relationship (e.g.,according to a predetermined pattern) relative to each other.

In forming the one or more web layers, the mono-functional ordi-functional species referenced herein may include a dihydric phenol, asecondary amine (e.g., a bis-secondary amine), a primary amine, or anycombination thereof. Any amine of the functional species can be anaromatic amine, an aliphatic amine or a combination thereof. Themono-functional or di-functional species may have one or twofunctionalities capable of reacting with epoxide groups to form agenerally non-cross-linked polymer. Some particular examples, withoutlimitation, of functional species for reaction with an epoxy moiety inaccordance with the present teachings includes an ethanolamine (e.g.,monoethanolamine), piperazine or a combination thereof. Any of theillustrative functional species may be substituted or unsubstituted.

Other examples of illustrative materials, functional species anddiepoxides are described in U.S. Pat. Nos. 5,115,075; 4,438,254;6,011,111; and WO 98/14498 (see e.g., pages 3-8) along with illustrativesynthesis conditions, all incorporated by reference herein (see alsoU.S. Pat. Nos. 3,317,471 and 4,647,648, also incorporated by referenceherein). Examples of such materials also can be found, withoutlimitation at paragraphs 15-25 of Published U.S. Patent Application No.20070270515 (Chmielewski et al), incorporated by reference for allpurposes.

The process for forming the web after initial polymerization of thethermoplastic epoxy material may be a melt spinning process, andelectrospinning process, a melt blowing process, or any process thatallows for depositing the web described herein onto a substrate, whichsubstrate may act to absorb the web when it dissolves during a moldingand/or curing process. Additives may be included in the web materialprior to or after the polymerization step. The formed web may then beapplied as a layer on a substrate into which the web material willeventually dissolve (e.g., a fibrous layer).

As shown for example in FIG. 1 , the processing system 10 may includeone or more fibrous layers 12 that receive one or more web layers 14therebetween. The alternating layers of fibrous material and webmaterial 16 can be located into a preform tool 18 where heat andpressure 20 are applied. The resulting stabilized preform 22 (e.g., thealternating layers of fibrous and web material post-heat application)can then be located into a mold 24. Once in the mold 24, it is possiblethat a resin material 26 is injected into the mold 24, over and aboutthe preform 22. A curing step 28 occurs, at which point the web layers14 dissolve into the adjoining fibrous layers 12. Post-cure, the curedcomposite 30 can be removed from the mold, forming the desired compositepart 32.

Example layers for forming the preform are shown in more detail at FIG.2 . More specifically, the fibrous layers 12 are shown in alternatingarrangement with the thermoplastic web layers 14. While the layers areshown as alternating, it is possible that multiple fibrous layers may bearranged in direct contact with one another, as may multiple web layers.

As shown for example at FIG. 3 , it is possible that on the material 34for forming the web layer 14 may be formed to contain one or moreadditives 36. The web layers 14 and fibrous layers 12 may be arranged inalternating (or some alternative fashion) to form the preform. Upondissolution of the web layers 14, the additive 36 becomes part of thefibrous layer 12.

EXAMPLES

The following Examples are illustrative of the teachings and are notintended as limiting. For the examples, viscosity of the resultingmixture in its green state (i.e., prior to cure) or in its post curestate, is measured according to ISO 6721-10:2015, at a temperature of170° C. at 11 radians/second (rad/s). Glass transition temperature ofthe post cured material is measured by differential scanning calorimetry(DSC) over a temperature range from 30 to 250° C. at a rate of 10°C./minute (min). Lap shear strength (reported as “shear strength”) ismeasured by ISO 4587:2003, following sandwiching of test compositionsbetween coupons of either degreased galvannealed 1010 steel or 2024aluminum. Surfaces of the coupons are prepared by degreasing (steel) orsanding (aluminum). Glass ball spacers are used for some samples tomaintaining spacing between sheets of metal. For some samples a Teflon®method is indicated, in which a polytetrafluoroethylene spacer is usedin lieu of the glass balls as a spacer.

Examples 1 and 2

For Examples 1 and 2, a thermoplastic epoxy material is prepared toinclude core-shell particulates (Kane Ace MX156 for Example 1, and KaneAce MX156 for Example 2). The thermoplastic epoxy material includes areaction product of diglycidyl ether of bisphenol A having an epoxyequivalent weight (g/eq) of about 184-190 (Kukdo YD 128k from KukdoChemical) and monoethanolamine. The results are shown in Tables 1 and 2,respectively. Three tests are run for each sample and an average (x) isreported.

TABLE 1 Components: Kukdo YD 128k + Kane Ace MX 156 (DGEBA suspensionmedium) Mono- Ethanolamine Ratio: 98 0% 10% 15% 20% 25% 35% 50% Coreshell (% by weight) 0.0% 2.0% 2.9% 3.7% 4.4% 5.7% 7.3% Post curing(After min. 5 hours at RT) 150° C. - 150° C. - 150° C. - 150° C. - 150°C. - 150° C. - 150° C. - 3 h 3 h 3 h 3 h 3 h 3 h 3 h Viscosity Essai 11210 2410 515 725 799 3090 3630 170° C. @ Essai 2 1330 2390 552 869 16103060 3660 11 rad/s (Pa · s) Essai 3 X X X X 2070 X X x 1270 2400 533.5797 1493 3075 3645 DSC (30-250° C., Tg 1st Heat (° C.) 70.4 70.9 69.468.8 71.1 71.6 70.4 250° C.-30° C., Tg 2nd Heat (° C.) 77.0 77.3 75.776.2 76.1 77.7 78.4 30° C.-250° C.: 10°/min) Shear strength Galva Test 111.20 14.00 11.00 8.02 10.80 16.70 16.80 (Mpa) @ RT G1010 Test 2 11.4011.80 8.54 8.59 17.20 14.90 20.90 (cure schedule (degrease) + Test 310.20 10.90 8.99 6.96 12.30 15.90 17.40 30 min @170° C.) bille de verrex 10.93 12.23 9.51 7.86 13.43 15.83 18.37 Alu Test 1 13.50 17.60 9.278.78 9.00 18.80 20.20 2024 Test 2 13.20 20.20 9.62 9.21 13.50 22.1023.40 (sand paper) + Test 3 14.40 13.50 11.60 8.59 15.00 18.20 21.40glass beads x 13.70 17.10 10.16 8.86 12.50 19.70 21.67 Galva Test 111.20 13.80 20.00 12.10 G1010 Test 2 8.09 15.00 17.50 13.80 (degrease)Test 3 10.90 14.20 16.20 12.50 Teflon x 10.06 14.33 17.90 12.80 Alu Test1 12.00 13.30 16.40 26.90 2024 Test 2 12.10 9.67 17.50 24.70 (sandpaper) Test 3 11.90 9.05 17.40 23.40 Teflon x 12.00 10.67 17.10 25.00

TABLE 2 Components: Kukdo YD 128k + Kane Ace MX 136 (DGEBF suspensionmedium) Mono- Ethanolamine Ratio: 98 0% 10% 15% 20% 25% 35% 50% 80% Coreshell (% by weight) 0.0% 2.0% 2.9% 3.7% 4.4% 5.7% 7.3% 9.7% Post curing(After min. 5 hours at RT) 150° C. - 150° C. - 150° C. - 150° C. - 150°C. - 150° C. - 150° C. - 150° C. - 3 h 3 h 3 h 3 h 3 h 3 h 3 h 3 hViscosity Essai 1 1210 683 1360 1500 609 707 1100 1280 170° C. @ Essai 21330 750 1450 2130 612 1040 1410 1270 11 rad/s (Pa · s) Essai 3 X X X X1840 2390 X X x 1270 716.5 1405 1815 1020.3 1379 1255 1275 DSC (30-250°C., Tg 1st Heat (° C.) 70.4 68.3 71.2 68.3 67.0 64.9 64.8 63.3 250°C.-30° C., Tg 2nd Heat (° C.) 77.0 74.4 74.3 73.8 73.2 72.4 71.6 70.430° C.-250° C.: 10°/min) Shear strength Galva Test 1 11.20 7.62 9.3418.20 11.70 13.10 14.10 20.50 (Mpa) @ RT G1010 Test 2 11.40 8.43 11.2012.50 9.95 13.10 12.50 19.00 (cure schedule (degrease) + Test 3 10.206.69 10.80 12.40 10.60 13.10 14.70 19.80 30 min @170° C.) bille de verrex 10.93 7.58 10.45 14.37 10.75 13.10 13.77 19.77 Alu 2024 Test 1 13.507.56 16.60 9.10 9.58 13.50 11.50 14.90 (sand paper) + Test 2 13.20 7.656.69 11.30 9.28 15.70 10.90 13.40 glass beads Test 3 14.40 8.74 13.4013.80 13.30 11.40 10.00 14.80 x 13.70 7.98 12.23 11.40 10.72 13.53 10.8014.37 Galva Test 1 11.20 10.50 17.70 12.40 20.80 G1010 Test 2 8.09 10.7017.00 15.00 24.60 (degrease) Test 3 10.90 12.00 17.40 14.10 26.50 Teflonx 10.06 11.07 17.37 13.83 23.97 Alu 2024 Test 1 12.00 13.50 11.20 19.4025.50 (sand paper) Test 2 12.10 11.30 11.40 10.70 25.40 Teflon Test 311.90 10.80 14.00 21.50 12.60 x 12.00 11.87 12.20 17.20 21.17

Examples 3 and 4

Examples 3 and 4 employ similar testing conditions as in Examples 1 and2. For Examples 3 and 4, a liquid epoxy resin reaction product ofbisphenol A and epichlorohydrin (Epikote 828 from Resolution PerformanceProducts) is employed. The liquid epoxy resin reaction product has anepoxy equivalent weight (g/eq) of about 184-190. Tables 3 and 4 provideresults.

TABLE 3 Components: EPIKOTE 828LVEL + Kane Ace MX 156 (DGEBA) MonoEthanolamine Ratio: 98 0% 20% 35% Core shell (% by weight) 0.0% 3.6%5.7% Post curing (After min. 5 hours at RT) 150° C. - 3 h 150° C. - 3 h150° C. - 3 h Viscosity Test 1 6350 23,300 5990 170° C. @ Test 2 696021,100 7290 11 rad/s (Pa · s) Test 3 x 20,600 6550 x 6655 21667 6610Analyze DSC (30-250° C., Tg 1st Heat (° C.) 74.5 75.6 73.5 250° C.-30°C., Tg 2nd Heat (° C.) 79.6 82.3 79.2 30° C.-250° C.: 10°/min) Shearstrength Galva Test 1 14.00 26.10 19.20 (Mpa) @ RT G1010 Test 2 16.2036.3 27.30 (cure schedule (degrease) Test 3 14.60 26.20 29.30 30 min@170° C.) scotch x 14.93 29.53 25.27 Alu 2024 Test 1 18.10 26.80 29.50(sand Test 2 16.30 26.70 28.90 paper) Test 3 18.20 24.50 31.70 scotch x17.53 26.00 30.03

TABLE 4 Components: EPIKOTE 828LVEL + Kane Ace MX 136 (DGEBF) MonoEthanolamine Ratio: 98 0% 10% 20% 35% Core shell (% by weight) 0.0% 2.0%3.6% 5.7% Post curing (After min. 5 hours at RT) 150° C. - 3 h 150° C. -3 h 150° C. - 3 h 150° C. - 3 h Viscosity Test 1 6350 7630 7290 6030170° C. @ Test 2 6960 7820 6820 5980 11 rad/s (Pa · s) Test 3 x x x x x6655 7725 7055 6005 Analyze DSC (30-250° C., Tg 1st Heat (° C.) 74.574.6 72.0 72.2 250° C.-30° C., Tg 2nd Heat (° C.) 79.6 78.4 76.8 75.630° C.-250° C.: 10°/min) Shear strength Galva Test 1 14.00 20.80 25.3027.40 (Mpa) @ RT G1010 Test 2 16.20 24.60 25.20 28.20 (cure schedule(degrease) Test 3 14.60 26.50 24.20 27.30 30 min @170° C.) scotch x14.93 23.97 24.90 27.63 Alu 2024 Test 1 18.10 27.80 28.70 19.70 (sandpaper) Test 2 16.30 24.10 29.20 19.60 scotch Test 3 18.20 24.10 28.6021.80 x 17.53 25.33 28.83 20.37

Example 5

Example 5 employs similar testing conditions as in Examples 1 through 4.For this example, a liquid epoxy resin as in Examples 1 and 2 isemployed. For this Example a different additive is employed. Table 5provides results. The additive is a colloidal silica dispersed in adiglycidyl ether of bisphenol F liquid suspension medium.

TABLE 5 Components: Kukdo YD 128k + Nanopox A 510 (DGEBF) MonoEthanolamine Ratio: 98 0% 10% 20% Core shell (% en masse 0.0% 3.2% 5.9%Post curing (After min. 5 hours at RT) 150° C. - 3 h 150° C. - 3 h 150°C. - 3 h Viscosity Test 1 1210 445 265 170° C. @ Test 2 1330 484 268 11rad/s (Pa · s) Test 3 X 385 388 x 1270 438 307 Analyze by DSC (30-250°C., Tg 1st Heat (° C.) 70.4 67.2 X 250° C.-30° C., Tg 2nd Heat (° C.)77.0 73.2 X 30° C.-250° C.: 10°/min) Shear strength Galva Test 1 11.206.03 5.94 (Mpa) @ RT G1010 Test 2 8.09 6.07 6.07 (cure schedule(degrease) Test 3 10.90 X X 30 min @170° C.) scotch x 10.06 6.05 6.01Alu 2024 Test 1 12.00 5.31 5.25 (sand Test 2 12.10 5.31 6.82 paper) Test3 11.90 7.77 5.66 scotch x 12.00 6.13 5.91

As used herein, unless otherwise stated, the teachings envision that anymember of a genus (list) may be excluded from the genus; and/or anymember of a Markush grouping may be excluded from the grouping.

Unless otherwise stated, any numerical values recited herein include allvalues from the lower value to the upper value in increments of one unitprovided that there is a separation of at least 2 units between anylower value and any higher value. As an example, if it is stated thatthe amount of a component, a property, or a value of a process variablesuch as, for example, temperature, pressure, time and the like is, forexample, from 1 to 90, preferably from 20 to 80, more preferably from 30to 70, it is intended that intermediate range values such as (forexample, 15 to 85, 22 to 68, 43 to 51, 30 to 32 etc.) are within theteachings of this specification. Likewise, individual intermediatevalues are also within the present teachings. For values which are lessthan one, one unit is considered to be 0.0001, 0.001, 0.01, or 0.1 asappropriate. These are only examples of what is specifically intendedand all possible combinations of numerical values between the lowestvalue and the highest value enumerated are to be considered to beexpressly stated in this application in a similar manner. As can beseen, the teaching of amounts expressed as “parts by weight” herein alsocontemplates the same ranges expressed in terms of percent by weight.Thus, an expression in the of a range in terms of “at least ‘x’ parts byweight of the resulting composition” also contemplates a teaching ofranges of same recited amount of “x” in percent by weight of theresulting composition.”

Unless otherwise stated, all ranges include both endpoints and allnumbers between the endpoints. The use of “about” or “approximately” inconnection with a range applies to both ends of the range. Thus, “about20 to 30” is intended to cover “about 20 to about 30”, inclusive of atleast the specified endpoints.

Use of (meth)acrylic or (meth)acrylate encompasses respectively anacrylic or methacrylic, or an acrylate or methacrylate.

The disclosures of all articles and references, including patentapplications and publications, are incorporated by reference for ailpurposes. The term “consisting essentially of to describe a combinationshall include the elements, ingredients, components or steps identified,and such other elements ingredients, components or steps that do notmaterially affect the basic and novel characteristics of thecombination. The use of the terms “comprising” or “including” todescribe combinations of elements, ingredients, components or stepsherein also contemplates embodiments that consist of, or consistessentially of the elements, ingredients, components or steps.

Plural elements, ingredients, components or steps can be provided by asingle integrated element, ingredient, component or step. Alternatively,a single integrated element, ingredient, component or step might bedivided into separate plural elements, ingredients, components or steps.The disclosure of “a” or “one” to describe an element, ingredient,component or step is not intended to foreclose additional elements,ingredients, components or steps.

It is understood that the above description is intended to beillustrative and not restrictive. Many embodiments as well as manyapplications besides the examples provided will be apparent to those ofskill in the art upon reading the above description. The scope of theinvention should, therefore, be determined not with reference to theabove description, but should instead be determined with reference tothe appended claims, along with the full scope of equivalents to whichsuch claims are entitled. The disclosures of all articles andreferences, including patent applications and publications, areincorporated by reference for all purposes. The omission in thefollowing claims of any aspect of subject matter that is disclosedherein is not a disclaimer of such subject matter, nor should it beregarded that the inventors did not consider such subject matter to bepart of the disclosed inventive subject matter.

What is claimed is:
 1. A composite article, comprising: i) at least onefibrous layer; and ii) at least one multiphase thermoplastic epoxy weblayer having a thermoplastic epoxy first phase and from greater than 0%by weight up to about 10% by weight of a discrete particulated secondphase of a core shell toughening agent dispersed throughout the firstphase and being separable from the first phase, wherein a dispersion ofparticulates of the toughening agent are dispersed in a suspensionmedium including bisphenol A, bisphenol F, another diepoxide or anycombination thereof with a diepoxide resin and an amine selected from amono primary amine, a di-secondary amine, or both to form an ingredientmixture; and wherein the web layer is located in direct contact with theat least one fibrous layer, the at least one thermoplastic epoxy weblayer being adapted to at least partially phase separate during amolding and/or curing process for releasing the second phase.
 2. Thecomposite article of claim 1, wherein the thermoplastic epoxy web layercomprises a reaction product of a polyhydroxy amino ether.
 3. Thecomposite article of claim 1, wherein the composite article issubstantially free of any liquid or powder adhesive and/or bondingmaterial.
 4. The composite article of claim 1, wherein the thermoplasticepoxy web layer dissolves during a molding and/or curing process bybecoming a fluidic material that is substantially entirely athermoplastic epoxy material, while the second phase remains in agenerally solid state, so that the additive and the fluidic material areseparable from each other.
 5. The composite article of claim 1, whereinthe at least one fibrous layer comprises a plurality of fibers in theform of a random distribution, a weave, a non-woven mat, a plurality ofgenerally axially aligned fibers, a plurality of axially intertwinedfibers, or any combination thereof.
 6. The composite article of claim 5,wherein the thermoplastic epoxy web includes a hydroxy-phenoxyetherpolymer reaction product of a mono-functional or di-functional specieswith a diepoxide, reacted under conditions for causing the hydroxylmoieties to react with the epoxy moieties to form a generally linearbackbone polymer chain with ether linkages.
 7. The composite article ofclaim 5, wherein the composite article includes an epoxy resin injectedabout the one or more fibrous layers and one or more thermoplastic epoxywebs during a molding process.
 8. The composite article of claim 1,wherein the thermoplastic epoxy web is dissolved within an epoxy resinso that the dispersed particulate toughening agent remains in place, incontact with the one or more fibrous layers.
 9. The composite article ofclaim 5, wherein the thermoplastic epoxy web includes amine end groupsand tertiary amines which react with the epoxy resin to increasecohesion between the at least one fibrous layers.
 10. The compositearticle of claim 1, wherein the composite includes exactly one fibrouslayer.
 11. The composite of claim, wherein the composite includes atleast two fibrous layers.
 12. A prepreg material including the compositearticle of claim
 1. 13. The composite article of claim 1, wherein thethermoplastic epoxy web layer includes a handling film.
 14. Thecomposite article of claim 1, wherein the thermoplastic epoxy web layerexhibits a lap shear strength, when bonded between opposing sheets ofaluminum or steel metal, per ISO 4587:2003 of at least about 5 MPa. 15.The composite article of claim 14, wherein the material has less thanabout twenty percent by volume of aggregates of particles of the coreshell toughening agent.
 16. The composite article of claim 14, whereinthe second phase is substantially uniformly distributed throughout thefirst phase.
 17. The composite article material of claim 1, wherein thecore shell toughening agent includes particulates having an elastomericcore and a shell including at least one meth (acrylic) acid, esterthereof, and/or nitrile thereof.
 18. The composite article of claim 17,wherein the toughening agent is characterized by an average particlediameter of about 0.01 micrometers to about 1 micrometers measured byscanning electron microscopy.
 19. The composite article of claim 17,wherein the toughening agent has a (T_(g)) glass transition temperaturethat is higher than the T_(g) of the first phase.
 20. The compositearticle of claim 1, wherein the composite article forms a structuraltape material.